Dithiocarbamate hydrochloride salts and their manufacture

ABSTRACT

N,N-disubstituted-N&#39;&#39; -arylamidino dialkyldithiocarbamate hydrochlorides are prepared by reaction of trisubstituted thioureas with disubstituted thiocarbamoyl chlorides. N,Ndisubstituted-N&#39;&#39;-arylamidino dialkyldithiocarbamate hydrochlorides are particularly useful as pre-emergent and contact herbicides.

United States Patent Olin [ Jan. 14, 1975 DITHIOCARBAMATE HYDROCHLORIDESALTS AND THEIR MANUFACTURE [75] Inventor: John F. Olin, Ballwin, Mo.

[73] Assignee: Monsanto Company, St. Louis, Mo. 22] Filed: July 24, 173

[21] Appl. No.: 382,259

Related US. Application Data [62] Division of Serv No. 160,556, July 7,1971,

abandoned.

[52] US. Cl. 260/479 C, 260/470, 260/479 R, 260/545 R, 71/98 [51] Int.Cl C07c 69/00 [58] Field of Search 260/455 A, 562 R, 545 R, 260/482 C,488 CD, 564 C, 479 C [56] References Cited UNITED STATES PATENTS3,138,628 6/1964 Sijpesteijr 260/455 A Primary Examiner-Leon ZitverAssistant Examiner'Gerald A. Schwartz Attorney, Agent, or FirmJ0hn L.Young 4 Claims, N0 Drawings DITHIOCARBAMATE HYDROCHLORIDE SALTS ANDTHEIR MANUFACTURE This is a division of application Ser. No. 160,556,filed July 7, 1971, now abandoned.

This invention relates to novel dithiocarbamate hydrochloride salts ofthe formula which dithiocarbamate hydrochloride salts of this inventionmay be readily prepared by reacting a trisubstituted thiourea of theformula with a disubstituted thiocarbamoyl chloride of the formulawherein R is naphthyl or wherein n is an integer of from to 3 and X ishalo, trihalomethyl, hydroxyl, lower alkyl, lower alkoxy, loweralkoxyalkyl, lower acylamido, lower alkacyl, lower alkylcarbamoyloxy oracyloxy of the formula C H COO wherein m is an integer of from 1 to 8,R, and R are each lower alkyl, lower alkenyl,-lower alkynyl or benzylhaving from 0 to 2 halo on thephenyl ring, and R and R are each loweralkyl or benzyl having from 0 to 1 halo on the phenyl ring.

Lower alkyl is alkyl having from 1 to 5 carbons. Examples of lower alkylinclude, but are not limited to, methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, isobutyl, tert-butyl, and pentyl. Preferred loweralkyl are ethyl and methyl.

Lower alkoxy have from 1 to 5 carbons. Examples of alkoxy include, butare not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy and theirisomers. Lower alkoxyalkyl have from 2 to 8 carbons, forexample,propoxymethyl, butoxybutyl, butoxyethyl, methoxymethyl andethoxypropyl.

Halo is a halogen selected fromthe group consisting of fluorine,chlorine, bromine and iodine. Preferred halo is chloro.

Lower alkenyl and lower alkynyl have from 2 through 5 carbons. Examplesof lower alkenyl include, but are not limited to, allyl and crotyl.Examples of lower alkynyl include, but are not limited to, 2- propynyl(propargyl), Z-butynyl, and 3-butynyl.

Lower alkacyl are represented by the expression, lower alkylCO. Loweracylamido are represented by the expression, lower alkylCONH-. Loweralkylcarbamoyloxy are represented by the expression, lower alkylNHCOO.

Products of this invention are useful as biocides. Exemplary of suchbiocidal uses for these products is the control of nematodes, arachnids,arthropods, molluscs and insects as well as eradication of noxiousweeds. Compounds of this invention are particularly useful aspre-emergent and contact herbicides.

Substituted thioureas and disubstituted thiocarbamoyl chlorides usefulin the process of the presentinvention for the preparation of the novelcompounds de scribed herein are known compounds which are commerciallyavailable or may be prepared by the skilled artisan by known methods.

Although the exact mechanism of the present process is not completelyunderstood, it is postulated that the chemical reaction proceeds asdescribed by the following chemical equation:

The reaction may be carried out at a temperature from about roomtemperature (approximately 20C.) to about 150C., but preferably fromabout 35C. to about C.

High yields and rapid reaction rates are obtained when the reaction isconducted under reflux conditions. When conducting the reaction atreflux the presence of an inert solvent is not necessary. Close controlof reaction conditions, particularly the amount of heat added to thereaction system, will allow conduct of the reaction at elevatedtemperatures without the presence of an inert solvent in a suitable openor closed vessel. It is advantageous, particularly in a commercialprocess, to conduct the reaction in a less strictly controlledenvironment. Therefore, it is'preferred to conduct the reaction atreflux in the presence of an inert solvent, and'morepreferred to conductthe reaction in the presence of an inert organic liquidwhich is asolvent for the reactants but not a solvent for the N,N-di-substituted-N'-arylamidino dialkyldithiocarbamate hydrochloride products of thereaction. The boiling of the inert solvent or inert organic liquid underrefluxprovides facile control of the reaction mass temperature.

Although conducting the reaction under reflux is preferred, the reactionmay also'be carried out in an open or closed vessel. Similarly, thereaction isgenerally promote the homogeneity of the reaction mass, it ispreferred to agitate the reaction mass during the course of thereaction, although agitation is not a necessary part of the presentprocess.

Although the described trisubstituted thiourea and disubstitutedthiocarbamoyl chloride will react regardless of the proportional amountsin which the two reactants are present, it is preferred that themolecular proportion of said disubstituted thiocarbamoyl chloride beapproximately equal to the molecular proportion of said trisubstitutedthiourea. It is more preferred that said disubstituted thiocarbamoylchloride be present at least in an equimolecular amount as compared tosaid trisubstituted thiourea, and still more preferred that saiddisubstituted thiocarbamoyl chloride be present in slight excess of anequimolecular amount.

The reaction mass may consist only of the aforedescribed reactants andtheir reaction products or it may contain other components in additionsuch as diluents, other inert materials and solvents, i.e., commonorganic liquids which are inert under the reaction conditions and whichmay dissolve one or more of the reactants or products of the reaction,which solvents are exemplified by but not limited to ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone, etc., aliphatichydrocarbons such as pentane, hexane, mineral spirits, etc., aromaticssuch as benzene, toluene, xylenes, etc., ethers such as diethyl ether,diisopropyl ether, etc., esters such as methyl acetate, ethyl acetate,propyl acetate, etc., and other organics such as tetrahydrofurane, etc.Preferred solvents are inert organic liquids which dissolve thereactants but not the desired reaction products which are products ofthis invention. Examples of preferred solvents are ketones, ethers andesters. More preferred solvents are ketones, ethers and esters withboiling points from about 35C. to about 100C. Preferably, the reactionis conducted under anhydrous conditions although small quantities ofwater may be present, up to about 2 percent by weight of the totalreaction mass. The presence of water does not prevent the reaction fromoccurring but causes hydrolysis of the disubstituted thiocarbamoylchloride which, in turn, decreases the yield of the desired products andresults in contamination of the reaction mass with fun HCl. R4"

As illustrative of this invention but not limitative thereof is thefollowing:

EXAMPLE 1 To a suitable reaction vessel equipped with an agitator,thermometer and reflux condenser are charged approximately 18 grams(g.), about 0.1 mole, of 1,1- dimethyl-3-phenyl-2-thiourea,approximately 12.4 g. (about 0.1 mole) of dimethylthiocarbamoyl chlorideand about 100 milliliters (ml.) of reagent grade acetone. The so-chargedvessel is heated to raise the temperature of the stirred reaction massto its boiling point. The particles of said thiourea dissolve giving alight straw-colored solution. Upon commencement of boiling of thesolution, a'solid precipitate appears. The mass is maintained at refluxfor about minutes. Thereupon an additional volume of acetone is added tothe mass, the mass is slurried and the precipitate is separated from theliquid by filtration. After washing twice with 50 ml. volumes of acetonethe white powder having a melting point of about 126 to 127C. is airdried and identified as N,N-dimethyl-N'-phenylamidinodimethyldithiocarbamate hydrochloride,

on en 3\ -N 3 ncl Calculated for C, H N S .HC1: C, 47.4; H, 6.0; C],11.7;

N, 13.8; S, 211 Found: C, 47.6; H, 6.2;C1, 11.);

EXAMPLE 2 To a suitable reaction vessel equipped with an agitator,thermometer and reflux condenser are charged approximately 18 g. (about0.1 mole) of 1,1-dimethyl-3- phenyl-2-thiourea, approximately 12.4 g.(about 0.1 mole) of diethylthiocarbamoyl chloride and about ml. ofreagent grade acetone. The so-chargcd vessel is heated to raise thetemperature of the stirred reaction mass to its boiling point. Theparticles of said thiourea dissolve giving a light straw-coloredsolution. Upon commencement of boiling of the solution, a solidprecipitate appears. The mass is maintained at reflux for about 10minutes. Thereupon an additional volume of acetone is added to the mass,the mass is slurried and the precipitate is separated from the liquid byfiltration. After washing twice with 50 ml. volumes of acetone the whitepowder with a melting point of about 129 to 130C. is air dried andidentified as N,N-dimethyl-N'- phenylamidino diethyldithiocarbamatehydrochloride,

N S CH C H 3 2 5 N-C-SC-N HCl CH3 C H Calculated for C H ,N:S .HC|: C,50.7; H, 6.7; S. 19.3 Found: C. 50.9; H, 6.8; S, 19.5

EXAMPLES 3 through 7 Utilizing the procedureof Example 2 butsubstituting for l,1-dimethyl-3-phenyl-2-thiourea an equimolecularproportion of the trisubstituted thiourea of Column A and substitutingfor diethylthiocarbamoyl chloride and equimolecular proportion of thedisubstituted thiocarbamoyl chloride of Column B the dithiocarbamatehydrochloride salt of Column C is obtained.

3-phenyl-2-thiourea thiocarbamoyl N'-phenylamidino chloridedi-(chloromethyU- dithiocarbamate hydrochloride 7 l, l -dipropyl-3-isobutylmethyl N,N-dipropyl-N naphthyl-Z-thiourea thiocarbamoylnaphthylamidino chloride isobutylmethyldithiocarbamate hydrochlorideEXAMPLE 8 To a suitable reaction vessel equipped with a thermometer,agitator and reflux condenser are charged approximately 62.3 g. (about0.25 mole) of 1-(3,4- dichlorophenyl)-3,3-dimethylthiourea and 200 g. ofchloroform. To the so-charged stirred mass is added approximately 33 g.of dimethylthiocarbamoyl chloride dissolved in 50 g. of chloroform overa period of minutes. The reaction mass is slowly warmed to boiling,giving a clear solution at about 50C. The mass is gently refluxed forabout one-half hour, cooled and evaporated using a rotary evaporator.The solid residue which is a white powder with a melting point of about159 to 162C. remaining is identified as N-(3,4-dichlorophenyl)-N,N-dimethylamidino dimethyldithiocarbamatehydrochloride,

Calculated for C H CI N S HCI: C, 38.7; H 4.3; S, [7

Found: C, 38.6; H, 4.3; S, l7.

EXAMPLE 9 To a suitable reaction vessel are charged approximately 18 g.(about 0.072 mole) of l-(3,4- dichlorophenyl)-3,3-dimethyl-2-thiourea,about 125 m1. of acetone and approximately 15.2 g. (about 0.1 mole) ofdiethylthiocarbamoyl chloride. The vessel is warmed sufficiently to givea clear solution of its contents and thereafter is allowed to cool toroom temperature, about 20C., and to remain at about that temperaturefor about 9 days. Thereafter, a crystalline product is separated fromthe reaction mass, washed twice with approximately 50 ml. volumes ofacetone, determined to be a colorless solid with a melting point ofabout 123 to 124C., and identified asN'-(-3,4-dichlorophenyl)-N,N-dimethylamidino diethyldithiocarbamatehydrochloride Calculated for C 4H Cl N S .HCl: C, 42.0; H, 5.0; S, 16.0Found: C, 42.]; H, 5.2; S, l5.9

EXAMPLES 10 through 23 Utilizing the procedure of Example 2 butsubstituting for l,1-dimethyl-3-phenyl-2-thiourea and an equimolecularproportion of the trisubstituted thiourea of Column A thedithiocarb'amate hydrochloride salt of Column B is obtained Example: A IB 10 l-( 3,4,5trichlorophenyl)- N'-(3,4,5-tr ichlorophenyl3,3-diisopropyl-2-thiourea N,N-diisopropylamidinodiethyldithiocurbuma'te hydrochloride 2,6-difluorophenyl)-N,N-dibutylamidino carbamule hydrochloride Example:

Continued l, l -dimethyl-3-(alpha, alpha,alpha,trifluorometatolyl)-2-thiourea N,N-dimethyl-N alpha,alpha,alpha-trifluorometatolyl)-amidino diethyldithiocarbamatehydrochloride l 1 ,1 -diethyl-3-(ortho- N,N-diethyl-N'-(orthotolyl)-2-thiourea tolyl)amidino diethyldithiocarbamatehydrochloride l,l-diisobutyl-3-( metacumenyl)-3-thioureaN,N-diisobutyl-N metacumenyl)-amidino diethyldithiocarbamateal1yl)-3-(3,4- dichlorophenyl)-2-thiourea N 3,4-dichlorophenyl)- amidinodiethyldithiocarbamate hydrochloride EXAMPLE 24 To a suitable reactionvessel equipped with a thermometer, agitator and reflux condenser arecharged approximately 19.6 g. (about 0.1 mole) ofl-(metahydroxyphenyl)-3,3-dimethyl-2-thiourea, approximately g. ofdimethylthiocarbamoyl chloride and about 100 ml. of dry acetone. Thevessel is heated to raise the temperature of the stirred contents toreflux. When the temperature reaches about 50C. a clear solution isobtained but as the temperature continues to rise clouding appears and asandy precipitate forms. After refluxing for about one hour, the vesselis allowed to cool to room temperature. The solid material is separatedfrom the liquid component by filtration, washed twice with about 35 ml.volumes of acetone, air-dried, determined to be a cream-colored solidwhich decomposes above about 135C., and identified as N,N-dimethyl-N-(meta-hydroxyphenyl)-amidino dimethyldithiocarbamatehydrochloride Calculated for C H N OS HG: C,

In similar fashion other N,N-disubstituted-N'- (hydroxyaryl)-amidinodialkyldithiocarbamate hydrochlorides such as hydroxyphenyl)-amidinodimethyldithiocarbamate hydrochloride,N-ethyl-N-methyl-N-(parahydroxyphenyl)amidino dimethyldithiocarbamate'hydrochloride, N,N-diethyl-N-(3,4-dihydroxyphenyl)- amidinodiethyldithiocarbamate hydrochloride, N,N-dimethyl-N'-(2,6-dihydroxyphenyl)-amidino diethyldithiocarbamatehydrochloride and the like may be prepared.

EXAMPLE 25 To a suitable reaction vessel equipped with a thermometer andreflux condenser are charged approximately 11.1 g. (about 0.05 mole) ofl-(paraacetylphenyl)-3,3-dimethyl-2-thiourea, about ml. of acetone andapproximately 7.4 g. (0.06 mole) of dimethylthiocarbamoyl chloride. Thevessel is heated to bring the contents to reflux temperature and thecontents are refluxed for about one-half hour. Upon cooling to roomtemperature a light tan precipitate appears which is separated from theliquid by filtration,

found to have an irregular melting point of about to C., and identifiedas N-(para-acetylphenyl)- N,N-dimethylamidino dimethyldithiocarbamatehydrochloride CH CO N S CH CH NC-SC-N 3 HCl CH3 CH3 Calculated for C HN;OS .l lCl1C, 48.6; H, 5.8; S, Hi5 Found: C, 48.5; H, 6.0; S. 18.4

In a similar manner other N,N-disubstituted-N- (acylphenyl)-amidinodialkyldithiocarbamate hydrochlorides such asN'-(meta-acetylphenyl)-N,N- diethylamidino diethyldithiocarbamatehydrochloride, N'-(ortho-acetylphenyl)-N,N-dimethylamidinodiethyldithiocarbamate hydrochloride,N'-(meta-propionylphenyl)-N,N-dimethylamidino dimethyldithiocarbamatehydrochloride, N'-(para-butyrylphenyl)-N,N-diethylamidinodiethyldithiocarbamate hydrochloride and the like may be prepared.

EXAMPLE 26 To a suitable reaction vessel equipped with a thermometer,agitator and reflux condenser are charged approximately 28 g. (about 0.1mole) of l,l-dimethyl- 3-(meta-pivalamidophenyl)-2-thiourea, about 100ml. of dry acetone and approximately 15 grams (about 0.12 mole) ofdimethyl carbamoyl chloride. The vessel is heated to bring the contentsto reflux and the contents are refluxed with stirring for about l/2hour. Thereafter to the clear, straw-colored solution is added about 75ml. of hexane. Upon cooling to about room temperature, approximately20C., the solution turns to a creamy white slurry. The precipitate isseparated from the liquid by slow filtration, washed alternately withsmall quantities of acetone and hexane, air-dried, determined to be anoff-white solid which decomposes at about 131C, and identified asN,N-dimethyl-N'- (meta-pivalamidophenyl)-amidino dimethyldithiocarbamatehydrochloride NHCOC (CH 3 N s CH3 N-C-S-C-N CH3 3 HCl Calculated for C HN OS .HCl: C, 50.7; H, 6.8; Cl, 8.8;

Found: c, 50.6; H, 6.9; or, 8.7; s. 15.8

EXAMPLE 27 To a suitable reaction vessel are charged approximately 14 g.(about 0.05 mole) of butyl para-(dimethylthiocarbamido) benzoatedissolved in about 100 ml. of dry acetone and approximately 7.4 g.(about 0.05 mole) of dimethylcarbamoyl chloride. The contents aremaintained at about room temperature (approximately C.) for about 3days. A copious precipitate forms which is separated from the remainderof the contents of the vessel, washed twice with ml. volumes of acetone,air-dried, determined to be an offwhite solid with an irregular meltingpoint of about 129 to 133C. and identified as butylpara-[(dimethylamino)mercaptomethylenelamino benzoate,dimethyldithiocarbamate hydrochloride N S CH CH 3\ N-C-S-CN 3 1 CH CH3Calculated for c u u o s ficlz C, 50.5; H, 6.5; s, 15.9 Found: C, 50.6;H, 6.6, s, 15.8

EXAMPLE 28 To a suitable reaction vessel are charged approximately 16.8g. (about 0.05 mole) of octyl para- (dimethylthiocarbamido)benzoatedissolved in about 100 ml. of dry-acetone and approximately 7.4 g.(about 0.05 mole) of dimethylcarbamoyl chloride. The contents aremaintained at about room temperature (approximately 20C) for about 3days. A copious white precipitate forms which is separated from theremainder of the contents of the vessel, washed twice with 25 ml.volumes of acetone, air-dried, determined to be a white solid with anirregular melting point of about 128 to 131C., and identified as octylpara- [(dimethylamino)mercaptomethylene]amino benzoate,dimethyldithiocarbamate hydrochloride CC )C H N 5 CH CH N-C'-S-C-N 3 HClca Calculated for Cz| N O S.HClI C, 54.8; H, 7.5; S, 13.7 Found: C,54.9; H, 7.7; S, 13 9 EXAMPLE 29 1, l -dimethyl-3-(meta-methylcarbamoyloxyphenyl 2-thiourea is prepared by charging to a suitableequipped reaction vessel about 32.7 parts by weight of 1,1-dimethyl-3-(metahydroxyphenyl)-2-thiourea, about 100 parts by weightof ethyl acetate, about 12 parts by weight of methyl isocyanate andabout 1 part by weight triethylamine, refluxing for about 1 hour withstirring, diluting the resulting slurry with about 100 parts by weightof hexane, cooling to about 20C., recovering the precipitate from theremainder by filtration, washing the recovered solid with ethyl acetateand hexane and air drying.

To a suitable reaction vessel equipped with reflux condenser, agitatorand thermometer is charged approximately 12.65 g. (about 0.05 mole) of1,1- dimethyl-3-(meta-methylcarbamoyloxyphenyl)-2- thiourea,approximately 10 g. of dimethylthiocarbamoyl chloride and about 100 ml.of reagent grade acetone. The vessel is heated to bring the contents toreflux temperature, about 60C., and the contents are refluxed withstirring for about one-half hour. Thereafter about ml. of hexane isadded to the hot mass. The mass is then cooled to about 15C. andfiltered to recover precipitated material from the remainder of thecontents. The recovered solid is washed with a mixture of 2 parts byvolume acetone and 1 part by volume hexane, air-dried, determined to bea colorless solid with a melting point of about 124 to 127C, andidentified as meta-[(dimethylamino) mercaptomethylene]aminophenylmethylcarbamate, dimethyldithiocarbamate hydrochloride ocNHcH Calculatedfor C H N O S .HCl: C, 44.6; H, 5.6; Cl, 9.4;

Found: C, 44.7; H, 5.6; CI, 9.4; N, 15.0

EXAMPLE 30 l-(meta-hydroxyphenyl)-3,3-dimethyl-2-thiourea,tertbutylcarbamate is prepared by charging to a suitable vessel about 25g. (approximately 0.1 mole) metahydroxyphenyl isothiocyanate,tert-butylcarbamate dissolved in about 150 ml. of methanol, and adding,with stirring about 15.4 g. (approximately 0.12 moles) of 40 percentaqueous dimethylamine mixed with about 50 ml. of methanol in a singleincrement. The mass quickly solidifies as the temperature rises fromabout room temperature to about 60C. The mass is cooled to about C.,separated from the residual liquid by filtration, washed with four 150ml. portions of a 75 percent methanol/25 percent water solution anddried under vacuum overnight.

To a suitable reaction vessel equipped with reflux condenser, agitatorand thermometer is charged approximately 25 g. (about 0.084 mole) ofl-(metahydroxyphenyl)-3,3-dimethyl-2-thiourea, tert-butyl carbamate,approximately 13.9 g. of diethylthiocarbamoyl chloride (about 0.092mole) and about 250 ml. of reagent grade acetone. The vessel is heatedwith stirring to bring the contents to reflux temperature, about 60C.,and the contents are refluxed with stirring for about 2% hours. Althoughthe slurry thins, solution is not achieved. The mass is then cooledovernight to about room temperature (approximately C.) and filtered torecover precipitated material from the remainder of the contents. Therecovered solid is washed with two 100 ml. portions of a mixture of 1part by volume acetone and 1 part by volume hexane, air-dried,determined to be a fluffy white powder with a melting point of about132C., and identified as meta- [(dimethylamino)mercaptomethylene]aminophenyl, tert-butyl carbamate,diethyldithiocarbamate hydrochloride ocmic (CH3) 3 5? N-c-s-c-N HCl 3 25 Calculated for C H N O,S .HC1: C, 51.0; H, 7.0; N, 12.5;

S, 14.3 Found: C, 51.1; H, 7.0; N, 12.6; S, 14.2

In similar manner other N,N-disubstituted-N-loweralkylcarbamoyloxyphenyl dialkyldithiocarbamate hydrochlorides maylikewise be prepared.

EXAMPLE 3 1 This example illustrates that the present method ofpreparation is not suitable for reactions based upon disubstitutedcarbamoyl (oxygen) chlorides of the formula The above procedure isrepeated except that, in

place of dimethylcarbamoyl chloride, about 9.4 g. (approximately 0.07mole) of diethylcarbamoyl chloride is charged to the vessel. Againstarting thiourea isrecovered and it is concluded that no reaction takesplace.

EXAMPLE 32 In greenhouse tests, seeds of 16 different plants, eachrepresenting a principal botanical type, were planted in 9-inch by13-inch by 2-inch aluminum pans which were level filled with theprepared soil. The soil was compacted to approximately three-eights inchbelow the top, 5 corn planted down the center with 5 soybeans on oneside and 5 cotton on the other. The grass species plus pigweed werescattered over A of the pan, broadleaf species were scattered on thenext A; and both barnyard grass and rice were planted in the remainingA; of the pan. A measured amount of barnyard grass and rice was plantedin rows (l0-20 seeds each). The seeds were covered with untreated soiland grown for contact use.

After the plants were 21 days old, each aluminum pan was sprayed with asolution of the candidate chemical. Each herbicidal solution wasprepared from an appropriate quantity of a 2 percent solution of thecandidate compound in dimethyl formamide diluted with acetone, 0.4 ml.ofa 3:1 cyclohexanone emulsifying agent mixture, and water to give avolume of 15 ml. of an emulsion of the concentration of the candidatecom pound shown in Table l. The emulsifying agent was a mixturecomprising 35 wt. percent butylamine dodecylbenzene sulfonate and 65 wt.percent of a tall oilethylene oxide condensate having about 6 moles ofethylene oxide per mole of tall oil.

The watering of the seeds was accomplished by placing the aluminum pansin a sand bench having one-half inch depth of water thereon andpermitting the soil in the pans to absorb moisture through theperforated bottom of the pans.

The planted pans were thereafter placed on a wet sand bench in agreenhouse and maintained there for 14 days under ordinary conditions ofsunlight and watering. At the end of this time, the plants were observedand the results recorded. The herbicidal rating was obtained by means ofa fixed scale based on the average percent germination of each seed lot.The herbicidal ratings are defined as follows:

No phytotoxicity.

Slight phytotoxocity. Moderate phytotoxicity. Severe phytotoxicity.Plants all dead Not tested.

Individual injury ratings for each plant type are re- EXAMPLE 34 portedin Table I.

Herbicidal solution concentrations of 0.2 percent, Pre-emergentherbicidal activity of representative N- 0.05 percent, and 0.01 percentare substantially equiv- ,N-disubstituted-N'-arylamidinodialkyldithiocarbaalent to application rates of 4 pounds per acre, 1pound mate hydrochlorides of this invention is determined by per acre,and 0.2 pound per acre, respectively. the following procedure: A goodgrade of top soil is TABLE I N 3, 1-dichlorophenyl LII Cotton CornSoybean Cocklebur Crab Grass Lambsquarter Wild Oat Smartweed BromePigweed Barnyard Grass Sugar Beet Wheat Velvet Leaf Rice Coffee WeedEXAMPLE 33 Contact herbicidal activity of representative N,N-disubstituted-N'-arylamidino dialkylthiocarbamate hydrochlorides of thisinvention is determined by the following procedure: The compound to betested is applied in spray form to plants of a given age of severalgrasses and broadleaf plants. After the plants are the desired age, eachaluminum pan is sprayed with a given volume of a 0.5 percentconcentration solution of the candidate chemical, corresponding to arate of approxi- 40 mately lbs. per acre. This solution is prepared froman aliquot of a 2 percent solution of the candidate compound in acetone,a known amount of cyclohexanoneemulsifying agent mix, and sufficientwater to make up to volume. The emulsifying agent is a mixture compris-45 placed in aluminum pans and compacted to a depth of three-eights toone-half inch from the top of the pan.

A pre-determined number of seeds of each of several plant species areplaced on top of the soil in the pans. The seeds are covered with soiland the pans leveled.

The herbicidal composition is applied by spraying the surface of the toplayer of soil with a solution containing a sufficient amount of activeingredient to obtain'a rate of application of 5 lbs. per acre. The pansare then placed on a sand bench in the greenhouse and watered from belowas needed. The plants are observed at the end of approximately 14 daysand the results recorded. Pre-emergent activity of the compoundsprepared in the designated Examples is observed against the species asshown in Table III. X denotes that herbicidal activity is observed. ing35 wt. percent butylamlne dodecylbenzene sulfonate and 65 wt. percent ofa tall oil-ethylene oxide con- TABLE III densate having about 6 moles ofethylene oxide per mole of tall oil. The injuries to the plants are thenobg s of l 2 8 9 served approximately 14 days later and the results aree recorded. Species Contact herbicidal activity of the compounds pre-Wild P X Morning Glory X X pared in the designated Examples is observedagainst Radish X X X the species as shown in Table II. X denotes thatherbisu ar lBeets X X X X oxtai X cldal activity 18 observed. Crabgms XX X X Pigweed X X X- TABLE H Wild Buckwheat X X Tomato X X Compound ofSorghum X X Example No. l 2 8 9 26 27 29 Soybean Y X Species Brome GrassMorning Glory X X X X X X X Wild Oat X X X X x I Rye Grass X X X Thecompounds of the present invention can be emjgf Q i. ployed in a methodof inhibiting the growth of un- Foxtail X X X X X X wanted vegetationwhlch comprises applying to the gf z g2 g2 area to be protected aherbicidally effective amount of l wee g x x X X X X the com ound. Sucha method ma utilize application Soybean p y *Vild ltmckwhea of thecompound to the SOll or directly to the foliage of S igliu in X X x X Xthe vegetation. Brome Grass X X X In using the compounds of the presentinvention as pre-emergent and contact herbicides, the compounds can beused alone or in combination with a material referred to in the art asan adjuvant in liquid or solid form. Herbicidal formulations areprepared by admixing the compound which is the active ingredient of theformulation with an adjuvant including diluents, extenders, carriers andconditioning agents to provide compositions in the form offinely-divided particulate solids, granules, pellets, solutions,dispersions or emulsions. Thus, the compounds of this invention arepreferably used with an adjuvent such as a liquid of organic origin and,if mixed within about an hour before application, water, a wettingagent, dispersing agent, an emulsifying agent or any suitablecombination of these. The herbicidal formulations usually contain fromabout 0.01 percent to about 99 percent by weight of the activeingredient. Application of these formulations to the soil or growthmedia can be carried out by simply admixing with the soil, by applyingto the surface of the soil and thereafter dragging or discing into thesoil to the desired depth, or by employing a liquid carrier toaccomplish the penetration and impregnation. The application ofherbicidal formulations to the surface of soil or to above groundportions of plants can be carried out by conventional methods, eg power,boom and hand sprayers. The formulations can also be applied fromairplanes as a spray because of their effectiveness at low dosages. In afurther method, the distribution of the active ingredients in soil canbe carried out by admixture with the water employed to irrigate thesoil. In such procedures, the amount of water can be varied with theporosity and water holding capacity of the soil to obtain the desireddepth of distribution of the active ingredients.

The exact amount of active ingredient to be employed is dependent uponthe response desired in the plant as well as such other factors as theplant species and stage of development thereof, the specific soil anddepth at which the active ingredients are distributed in the soil andthe amount of rainfall as well as the specific active ingredientemployed. In foliar treatment, the active ingredients are applied inamounts from about 1 to about 50 or more pounds per acre. Inapplications to soil for the control of the growth of germinant seeds,germinative seeds, emerging seedlings and established vegetation, theactive ingredients are applied in amounts from about 0.1 to about 25 ormore pounds per acre. It is believed that one skilled in the art canreadily determine from the teachings of this specification the generalprocedure for any application.

While this invention has been described with respect to certainembodiments it is to be understood that it is not so limited and thatvariations and modifications thereof obvious to those skilled in the artto which this invention appertains can be made without departing fromthe spirit or scope thereof.

What is claimed is: l. A compound of the formula 0 C lower alkyl) R N SR 1 II I 3 BN-C-S-C-NI HCl R; R4

wherein R R R and R are each lower alkyl and n is an integer from 1 to3.

2. A compound of claim 1 wherein the lower alkyl is methyl or ethyl.

3. The compound of claim 2 which is meta-[(dimethylamino)mercaptomethylene]aminophenyl methylcarbamate,dimethyldithiocarbamate hydrochloride.

4. The compound of claim 2 which is meta-[(dimethylamino)mercaptomethylenelaminophenyl, tert-butyl carbamate,diethyldithiocarbamate hydrochloride.

2. A Compound of claim 1 wherein the lower alkyl is methyl or ethyl. 3.The compound of claim 2 which is meta-((dimethylamino)mercaptomethylene)aminophenyl methylcarbamate, dimethyldithiocarbamate hydrochloride. 4.The compound of claim 2 which is meta-((dimethylamino)mercaptomethylene)aminophenyl, tert-butyl carbamate, diethyldithiocarbamate hydrochloride.